Chemical compounds containing sulfur and spirobi (meta-dioxane) groups



United rates Patent 3,043,850 CHEMICAL COMPOUNDS CGNTAINING SULFUR ANDSPIROBI (META-DIOXANE) GROUPS Howard R. Guest, Charleston, Joe T. Adams,St. Albans, and Harry A. Stansbury, Jr., South Charleston, W. Va.,assignors to Union Carbide Corporation, a corporation of New York NoDrawing. Original application Sept. 26, 1957, Ser. No. 686,277, nowPatent No. 2,996,516, dated Aug. 15, 1961. Divided and this applicationApr. 26, 1960, Ser. No. 27,236

3 Claims. (Cl. 260-3401) This invention relates to novelspirobi(meta-dioxane) derivatives and their preparation. In one aspect,this invention relates to a method of producing chemical compoundscontaining spirobi(meta-dioxane) and sulfur groups. ,In another aspect,this invention relates to chemical compounds containing substitutedspirobi(metadioxane) and sulfur groups'which are useful as intermediatereactants and as accelerators for curing rubber.

This application is a division of application S.N. 686,- 277, filedSeptember 26, 1957, now Patent 2,996,516.

It is an object of the present invention to provide a method forproducing chemical compounds Containing spirobi(meta-dioxane) and sulfurgroups.

It is a further object of this invention to provide spirobi-(meta-dioxane)- and sulfur-containing chemical compounds which haveactive sites that can react under suitable conditions.

Other objects and advantages of the present invention will becomeapparent to those skilled in the art from the following description.

The compounds according to this present invention are produced byreacting together a '3,9-divinylspirobi(metadioxane) compound and amercaptoalcohol having available at lease one thiol group and one.hydroxyl group.

The 3,9-divinylspirobi(meta-dioxane) compounds preferred are thosehaving the formula:

CH2 CH2O\ D-CE /C EC-D wherein -D is selected from the group consistingof (R--CH =CH) and UHF-C- and R is selected from the group consisting ofhydrogen, halogen and lower alkyl.

The 3,9-divinylspirobi(meta-dioxane) compounds which are mostconveniently and economically prepared from widely available startingmaterials are those which have hydrogen or a methyl substituted on eachvinyl group. The 3,9-divinylspirobi(meta-dioxane) compounds whichcontain groups other than hydrogen and methyl substituted on the vinylgroups are sometimes more difficult to prepare. These other groups mustbe of a character and in a position on the vinyl groups not to interferewith the effective reactions of 3,9-divinylspirobi(meta-' by thecondensation of a mole of pentaerythritol with two moles of acrolein oran acrolein derivative in the presence of an acid catalyst such asp-toluenesulfonic acid. This well-known synthetic method is published indetail in Schulz and Wagner, Angew. Chemie 62, 118 (1950), and in GermanPatents 858,406; 870,032 and 885,006.

The 3,9 divinylspirobi(meta dioxane) compounds which contain terminalmethylene groups are derived from the reaction of pentaerythritol witha,,B-unsatll1'at6d aldehyde such as acrolein, alpha-methyl acrolein,alphaethyl acrolein, alpha-propyl acrolein, alpha-butyl acrolein,alpha-isobutyl acrolein and the like.

When acrolein is used, an unsubstituted 3,9-divinylspirobi(meta-dioxane)is obtained:

HOCH: CHQOH HOOH: OH OH OCH:

OHQ=CHOE C\ 9 Do CHaO When the condensation is conducted with (a) alpha-CHzO -' methyl acrolein or (b) crotonaldehyde, then methyl-sub stituted3,9-divinylspirobi(meta-dioxanes) are obtained: (a) 0113 H0011. onion vH+ 2OH2=C CHO G HO OH: 0111011 CH3 OCHz. CH20\ CH3 CH2: 0 /0 /oH0=oH,

(0) HO 0 H, 0 Hi0 H H+ 2CH3CH=OHOHO /C --v HO CH2 OH2OH /O C H2 C 1120CH3CH=GHCH C GHCH=CHCH3 It is not necessary that the O B-unsaturatedaldehyde reacted with pentaerythritol be pure or a single species.Mixtures of n p-unsaturated aldehydes may be condensed withpentaerythritol for purposes of convenience and economy. The resultingproducts are mixtures of 3,9-divinylspirobi(meta-dioxane) compoundswhich may be used in their crude form directly in the processes of thisinvention.

The mercaptoalcohols that are useful in this invention are those whichcontain at least one 'thiol group and one The reaction of amercaptoalcohol and a 3,9-divinylspirobi(meta-dioxane) compound proceedswell under moderate conditions. The reaction temperature may varybetween about room temperature and 200 C., with a preferred temperaturerange being between and 120 the nature of the reactants and on thereaction conditions.

. mercaptan groups are present then polymerization may reactivity of thehydroxyl group and the mercaptan group.

i a mercaptoalcohol with a 3,9-divinylspirobi(meta-dime 3,043,850 t C.Atmospheric pressure is satisfactory for most of the rubber and asintermediates for the production of other reactions, or autogenouspressure it the reaction is cOnchemicals. The reactive sites, e.g.,hydroxyl, mercaptan, ducted in a closed system. Either batchwise orconsulfide, acetal, etc., make the compounds susceptible to tinuousmethods may be employed. The reaction time chemical transformation. mayvary between about 0.1 and 20 hours depending on The mole ratio ofmercaptoalcohol to 3.9-divinyl-spirobi(meta-dioxane) may vary between 5moles of mercaptoalcohol to each mole of spirobi-compound, and 0.5 moleof mercaptoalcohol to each mole of spirobi compound. An excess ofmercaptoalcohol compound favors ture or combination of thesulfur-containing compounds with said materials.

The following examples will serve to illustrate particular embodimentsof this invention.

a simple addition product, While an excess of3,9-divinylspirobi(meta-dioxane) increases the possibility ofa poly-EXAMPLE 1 merization reaction, the latter being especially true at OCH2OHIO higher temperatures and in the presence of an acid catalyst such asp-toluenesulfonic acid, sulfuric acid, and CHFC HCCHZCH HOCHOHSH zincchloride. 0 on: 011.0

A solvent is not ordinarily necessary, but if it is desired 3,9divinylspirobl(meta-dioxane) monothioethyleneglycol one may be employed,e.g., benzene, dioxane, tetrahydro- (z'memapmeihaml furan,ethyleneglycol diether ether, dibutyl ether, hep- Gem CHZO tane,dimethylformamide, and the like. A solvent may be preferable when aninorganic acid catalyst is being HOGHCHQSCIHG used. 00 1 OHQO Anillustration of the production of the novel corn-3,9-bis(2-hydroxyethylmercaptoethyl)spirobi(meta-dioxane) pounds of thisinvention'is the reaction of 1,3-dithioglycerol with3,9-(a,a'-dimethy1)divinylspirobi(metadioxane) under conditions whichfavor polymerization:

OH: OCH: CHzO CH3 HO CzHrSGHzCEhOH A mixture of3,9-divinylspirobi(rneta-dioxane) (42 grams, 0.2 mole) andmonothioethyleneglycol (31 grams,

00%: CHzO 11 Another illustration is the reaction of monothiodieth- 0.4mole) were introduced into a glass reaction flask yleneglycol with3,9-(fi,B-dimethyl) divinylspirobi(meta'- equipped with a stirrer and areflux condenser and heated dioxane) under conditions which yieldaddition prodat a temperature of 120 C. for one hour. The reaction ucts:mixture components which were volatile at a temperature HSOHNHBOCHQOHQOH40 of 200. C./0.5 mm. were removed by distillation, and anoomomoornonzs-oani-n-oinu-scniongocnicnzorr+ g i s z ggg g lCH:=CHRCaH0-'SCH2CH OCHZCH2OCsHrR-CH=OH2+ a mo ecu Welg t Y e Memes HOGHOH OCH CH S C H R H OCH H OCH CH SH Wright method (theory for productformula above: 368),

2 2 3 .B so 2 and 103.1% purity 1 by analytical phthalation(deterwherein (-R-) is p mines both hydroxyl and thiol groups). Ananalysis of CH) thiol groups by oxidation with iodine was performed andE E it indicated that 32.8% by Weight of the product was 3,9 bis(2mercaptoethoxyethyl)spirobi(meta-dioxane). CHQO These results showthatabout two-thirds of the double The' mercaptoalcohol reactantsdescribed in this inbonds in the divinyl compounds added the thiol groupand vent-ion have at least two functional positions, i.e., a thiolapproximately one-third added the hydroxyl group. group and a hydroxylgroup. As mentioned previously, simple addition or polymerization mayoccur. When only EXAMPLE 2 one fa Q P is Present in the mercaptoalcohol90% 3,9-'divinylspirobi(meta-dioxane) (236 grams, 1.0 then addltionreactions predominate. When two or more mole) and pmmenesulfonic acidcatalyst O gram) were placed in a glass reaction flask equipped with astirrer, feed tank and reflux condenser and heated at a temperature of9095 C. with stirring. Monothioethbe induced more easily. This is due tothe diiference in The hydroxyl group is a weaker base than themercaptan. group, i.e., the mercaptan group is more nucleophilic thanthe hydroxyl group, hence, a mercap-tan group more readily forms a bondwith an electron-deficient carbon 1 atom than does a hydroxyl group.

From the foregoing description it is apparent that complexproductrnixtures may result from the reaction of ture over a period ofthirty minutes. After a reaction time of seven hours at a temperature of95 C., the acid catalyst was neutralized by the addition of anhydroussodium acetate (3.0 grams), and the reaction mixture components whichwere volatile at a kettle temperature of 89 C./ 3 mm. were removed bydistillation to yield a residual product (345 grams) which had amolecular weight of 401 by the Menzies-Wright method.

EXAMPLE 3 This example illustrates the eifective use of a product ofthis invention as an accelerator for the vulcanization of naturalrubber.

ane). The potential or actual variety of products is due to thepolyfunctionality of the reactants, and also due to the fact that thereare two modes of addition to each of the vinyl groups in thespirobi(meta-dioxane) compound which increases the number of possibleisomers.

The products of this invention have wide application in the chemicalfield. The unique properties exhibited by these sulfur-containingspirobi(meta-dioxane) derivafives make them applicable as acceleratorsfor curing 7 unusual results for some analytical procedures.

The properties of these liquid and solid sulfur-contain-- ing compoundscan be imparted to other materials such as natural andsynthetic polymersand elastomers by mixylleneglycol (156 grams, 2 moles) was added to themix- Percentages slightly higher than one hundred are not I FormulationsCompounded 5 Minutes at 75 to 90 C. on a Two-Roll Mill (a) 100 gramsnatural rubber (smoked sheet) 1 gram Age Rite powder 5 grams zinc oxide2 grams sulfur 3 grams stearic acid 50 grams Kosmobile 77EPC carbonblack. (b) Same as (a) except 1 gram of the product described in Example2 was added.

Both (a) and (b) were cured (vulcanized) for 60 min- Too soft andflexible for testing.

Having described our invention, we claim:

1. A process for producing resins containing sulfur andspirobi(meta-dioxane) groups which comprises reacting a3,9-divinylspirobi(meta-dioxane) compound with a mercaptoalkanol havingbetween two and ten carbon atoms and having at least one reactive thiolgroup and at least one reactive hydroxyl group at a temperature betweenC. and C. in the presence of an acid catalyst, at a molar ratio of3,9-divinylspirobi(metadioxane) compound to mercaptoalkanol of at leastone said 3,9-diviny1spirobi(meta-dioxane) compound having the formula:

OCH: CH20\ D-C C HC-D wherein D is selected from the group consisting of(RCH=CH-) and and R is selected from the group consisting of hydrogen,halogen and lower alkyl.

2. The process of claim 1 wherein said 3,9-divinylspirobi(meta-dioxa.ne)compound is 3,9-divinylspirobi- (meta-dioxane) and said mercaptoalkanolis Z-mercaptoethanol.

3. The resins produced by the process of claim 1.

No references cited.

1. A PROCESS FOR PRODUCING RESINS CONTAINING SULFUR ANDSPIROBIC(META-DIOXANE) GROUPS WHICH COMPRISES REACTING A3,9-DIVINYLSPIROBI(META-DIOXANE) COMPOUND WITH A MERCAPTOALKANOL HAVINGBETWEEN TWO AND TEN CARBON ATOMS AND HAVING AT LEAST ONE REACTIVE THIOLGROUP AND AT LEAST ONE REACTIVE HYDROXYL GROUP AT A TEMPERATURE BETWEEN30*C. AND 150*C. IN THE PRESENCE OF AN ACID CATALYST, AT A MOLAR RATIOOF 3,9-DIVINYLSPIROBI (METADIOXANE) COMPOUND TO MERCAPTOALKANOL OF ATLEAST ONE SAID 3,9-DIVINYLPIROBI(META-DIOXANE) COMPUND HAVING THEFORMULA: